CN101573467B - Plasma surface treatment using dielectric barrier discharges - Google Patents

Plasma surface treatment using dielectric barrier discharges Download PDF

Info

Publication number
CN101573467B
CN101573467B CN2007800366020A CN200780036602A CN101573467B CN 101573467 B CN101573467 B CN 101573467B CN 2007800366020 A CN2007800366020 A CN 2007800366020A CN 200780036602 A CN200780036602 A CN 200780036602A CN 101573467 B CN101573467 B CN 101573467B
Authority
CN
China
Prior art keywords
particle
dielectric barrier
barrier discharge
coating
torch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2007800366020A
Other languages
Chinese (zh)
Other versions
CN101573467A (en
Inventor
马厄·I·布洛斯
乌尔里克·科格尔沙茨
克里斯廷·内西姆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tekna Plasma Systems Inc
Original Assignee
Tekna Plasma Systems Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tekna Plasma Systems Inc filed Critical Tekna Plasma Systems Inc
Publication of CN101573467A publication Critical patent/CN101573467A/en
Application granted granted Critical
Publication of CN101573467B publication Critical patent/CN101573467B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
    • H05H1/2443—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube
    • H05H1/246—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube the plasma being activated using external electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
    • H05H1/2443—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube
    • H05H1/2465—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube the plasma being activated by inductive coupling, e.g. using coiled electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/083—Details relating to the shape of the electrodes essentially linear cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0837—Details relating to the material of the electrodes
    • B01J2219/0841—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0869—Feeding or evacuating the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0879—Solid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • B01J2219/0896—Cold plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Abstract

A process for the in-flight surface treatment of powders using a Dielectric Barrier Discharge Torch operating at atmospheric pressures or soft vacuum conditions is described herein. The process comprising feeding a powder material into the Dielectric Barrier Discharge Torch yielding powder particles exhibiting a reduced powder agglomeration feature; in-flight modifying the surface properties of the particles; and collecting coated powder particles. An apparatus for surface treating micro- and nanoparticles comprising a Dielectric Barrier Discharge Torch operating at atmospheric pressure or soft vacuum conditions is also described herein.

Description

Utilize the plasma surface treatment of dielectric barrier discharge
Technical field
The present invention relates to micron particle and nanoparticle carried out plasma surface treatment by means of dielectric barrier discharge (dielectric barrier discharge).More specifically but not exclusively, (Dielectric Barrier DischargeTorch DBDT) applies the method for micron particle and nanoparticle to the present invention relates to dielectric barrier discharge torch through under normal atmosphere or rough vacuum condition, working.The invention still further relates to the equipment that applies micron particle and nanoparticle, this equipment is included in the dielectric barrier discharge torch of working under normal atmosphere or the rough vacuum condition.
Background technology
Nanometer powder has the unique physical character directly related with its small size and high-specific surface area.Nanometer powder has inherent and assembles tendency, and this causes its apparent particle size to increase.Gathering has direct influence to the functional of nanometer powder like its optics and magnetic properties and catalysis and conductive properties.
Nanometer powder greatly very easily reacts because of its specific surface area and is difficult to and handles.The outside surface that film or other coating material is deposited on each particle stops aggregation of particles also for particle safe processing to be provided under the situation of not sacrificing the particle peculiar property.
Coating material is that the surface property that is chosen as powder of polymer-type or other type coating material provides selective control.Through powder being carried out surface treatment and/or, except controlling other intrinsic property, also can changing the wetting ability of powder through suitably selecting coating material.Can form stable spontaneous combustion nanometer aluminium powder (igniting easily at ambient temperature) through polymeric film is applied to particle surface.This coating provides stable at a lower temperature powder, the high calorie value of powder under comparatively high temps is not caused disadvantageous effect simultaneously.
Previous using plasma surface treatment strengthens the hydrophobicity, wetting ability, tack and the erosion resistance that comprise the multiple base material of polymeric film as surface modifying method.In addition, plasma surface treatment also is widely used in cleaning and etch application.
Plasma-deposited method and Plasma Polymerization have been developed, so that shallow layer such as polymeric film are applied to various base materials.These methods are mostly in quite low pressure (less than 100Pa) work down.
Before reported thin film coated, and, reduced the gathering of nanometer powder simultaneously and improve the dispersiveness of nanometer powder in order to change the surface properties of nanometer powder.People such as He have reported and have used the RF plasma torch (27MHz) of working down in low pressure (30Pa) that polyethylene film is coated on zirconium white (ZrO 2) nanometer powder (～130nm) (1).
People such as Shi have reported and have used the RF plasma torch (13.56MHz) of working down in low pressure (25Pa) that polypyrrole film is coated on aluminum oxide (Al 2O 3) nanoparticle (～10-150nm) (2).Discharge power deposition polypyrrole film with 10W.Use the fluidized-bed that keeps vacuum to introduce aluminium oxide nano powder (0.16g/min).People such as Shi have also reported and have adopted similar method that Polystyrene Film is deposited on carbon nanotube (3).
People such as Schallehn reported use low pressure (1kPa) down the RF plasma torch (13.56MHz) of work the ethyl group polymer layer of thick about 1.5nm is coated on aluminum oxide (Al 2O 3) nanoparticle (4).Through the aluminum oxide (Al that applies 2O 3) nanoparticle generates with the productive rate of the speed of 0.5-1g/h and about 40%.
People such as Vollath have reported microwave (MW) plasma torch of work under high frequency (2.45GHz) and low pressure (1-5kPa), come coated with nano oxide powder such as zirconium white (ZrO 2), aluminum oxide (Al 2O 3), Tungsten oxide 99.999 (WO 2, WO 3), hafnia (HfO 2), White tin oxide (SnO, SnO 2) and red stone (Fe 2O 3) (5,6).Use TEB 3K to realize the coating of film as polymer precursor.Monomer is introduced in discharge exit in plasma torch, and makes monomer polymerization under the UV radiating effect that plasma body sends.
People such as Lik Hang Chau have reported the preparation of Nano silver grain and have used the MW plasma torch of under high frequency (2.45GHz) and low pressure, working with the coating (7) of polymer layer to Nano silver grain.This author has also reported the preparation of cobalt nanometer particle and has used the MW plasma torch with the coating (8) of silicon carbide layer to cobalt nanometer particle.CoCl 2And SiCl 4/ hexane is respectively to be used to the precursor for preparing and apply.
People such as Kouprine have described and have used the condenser type plasma torch (13.6MHz) of working down in low pressure (1-5kPa) to apply the fine silica (9) of size range as 30-80nm.The plasma discharge power setting is 700-1500W, and plasma gas is made up of the mixture of argon gas and methane or ethane.Use fluidized-bed to introduce the silicon dioxide powder powder stock.
People such as Dumitrache have reported the synthetic of Fe nanometer particles and have used continuous wavelength CO 2Laser apparatus applies the carbon that nanoparticle carries out through laser pyrolysis iron, and this laser apparatus is with the set value of the power of 120W, 10.6 microns wavelength (λ) and the pressure work (10) of 700mbar.Iron carbonyl and acetylene are respectively and are used for the precursor that powder is synthetic and apply.
People such as Ermoline have reported the synthetic of aluminum particulate and have used the DC plasma body arc discharge torch (1-50V that under atmospheric pressure works; The carbon that 30-150A) aluminum particulate is carried out applies (11).It is reported that negative electrode is made up of copper, anode is made up of consumable aluminium bar.Anodic is ablated and is carried out with pulse mode, to produce the nano aluminum particle through applying.Use Sweet natural gas to realize that carbon applies.
People such as Sawada have reported at custom-designed plasma discharge torch (15kHz; 100kPa; Utilize 10W) Atomospheric pressure glow discharge (APGD) with plasma polymerization tetrafluoroethylene (TFE) thin film coated in porous and granular silicon dioxide granule (～150 μ m) (12).Plasma body unstripped gas is made up of helium and TFE (1%).It is reported that the silicon dioxide granule circulation is through the plasma slab several times.
People such as Lei have reported that using the DBD torch of under atmospheric pressure working that copper nano-particle is carried out carbon applies (13).Copper nano-particle adopts from oriented flow method (the flow levitation method) preparation that suspends, and wherein uses high-frequency electromagnetic induction circle heating copper cash.Subsequently, through DBD torch original position prepared copper nano-particle is carried out carbon and apply, this DBD torch uses argon gas, hydrogen and methane and works down in normal atmosphere.
People such as Bretagnol have studied the surface-treated of new LDPE (film grade) (LDPE) powder in low pressure RF plasma body, and this low pressure RF plasma body is worked with 13.56MHz and used nitrogen and ammonia as handling gas (19).Powder circulates in fluidized-bed reactor.In order to change the wettability of particle, need about 300 seconds residence time.
As people such as Leroy are said polyethylene powders (20) have been carried out handling.Make plasma discharge be coupled to fluidized-bed reactor and in the twilight sunset district of plasma body, handle powder.Handling gas is the mixture of oxygen and nitrogen.Frequency of utilization is the microwave plasma of 2450MHz, and under 0.1 to 20mbar low pressure, works.
The present invention is with reference to lot of documents, and the full content that is incorporated herein them as a reference.
Summary of the invention
The present invention relates to surface treated micron and/or nanometer particle process method.In one embodiment, the present invention relates to use the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working to prepare the method for surface treated micron particle and nanoparticle.In the surface-treated typical embodiments, the present invention relates to change the method for the surface chemical property of micron and/or nanoparticle through the plasma discharge effect.More in the typical embodiments, the present invention relates to change the method for the surface chemical property of micron and/or nanoparticle at surface-treated through the deposition coating material.
In one embodiment, the present invention relates to micron particle and nanometer particle process method, wherein the thickness of control coating (being film) advantageously through applying.The thickness range of coating is generally less than 1 nanometer to hundreds of nanometers.
More specifically, such as summary advocates, the present invention relates to use the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working that powder particle is carried out the surface-treated method, this method comprises: (a) powder stock is sent into the dielectric barrier discharge torch; (b) pass through the surface chemical property that the plasma discharge effect changes powder stock; Reach and (c) collect surface treated particle.
More specifically, such as summary advocates, the present invention relates to powder particle is carried out the surface-treated method, this method comprises: (a) the granular powder material is sent into dielectric barrier discharge torch assembly; (b) particle in the dielectric barrier discharge torch is carried out surface-treated awing, produce surface treated particle; Reach and (c) collect surface treated particle.In embodiments of the invention, modification awing comprises particle surface is acted on plasma discharge mutually.In another embodiment of the present invention, modification awing comprises: through coating material precursor injected media barrier discharge torch assembly is generated coating material; Reach coating material is deposited on particle surface and produces the particle through applying.
More specifically; Such as summary advocates; The present invention relates to by means of the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working powder particle carried out the surface-treated method, this method comprises: (a) powder stock is introduced the dielectric barrier discharge torch; (b) at least a finish materials is introduced dielectric barrier discharge torch, the surface treated powder particle of this material production; Reach and (c) collect surface treated particle.
More specifically; Such as summary advocates; The present invention relates to powder particle carried out the surface-treated method by means of the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working; This method comprises: (a) at least a finish materials precursor is introduced the dielectric barrier discharge torch, produce coating substance; (b) coating substance is contacted with powder stock; Reach and (c) collect surface treated powder particle.
More specifically; Such as summary advocates; The present invention relates to by means of the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working powder particle carried out the surface-treated method, this method comprises: the atomized liquid raw material that (a) will comprise dispersed powders and at least a finish materials precursor is introduced the dielectric barrier discharge torch; Reach and (c) collect surface treated powder particle.
In one embodiment, the present invention relates to be included in the equipment of the dielectric barrier discharge torch of working under normal atmosphere or the rough vacuum condition, this equipment is used to produce surface treated micron particle and nanoparticle.
In one embodiment, the present invention relates to powder particle carried out surface-treated equipment awing, this equipment comprises:
The dielectric barrier discharge torch, it comprises: first inlet that (i) is used for plasma gas is sent into said torch; (ii) be used for the granular powder material is sent into second inlet of said torch; Reach the discharge chamber that (iii) is used to handle the granular powder material, this reaction chamber comprises the electrode structure that is arranged in its outside surface; And
Collect the device of surface treated particle;
Wherein, through making the gas that forms plasma body produce plasma discharge through discharge chamber; The surface-treated to particle is facilitated in-flight in the discharge of this plasma body.
The invention still further relates to surface treated micron particle and nanoparticle.In one embodiment, the present invention relates to have the micron particle or the nanoparticle of organic coating.In one embodiment, the present invention relates to have the micron particle or the nanoparticle of inorganic coating.In one embodiment, the present invention relates to have the micron particle or the nanoparticle of metallic coating.In typical embodiment, the present invention relates to have the micron particle or the nanoparticle of oxide coatings.In another typical embodiment, the present invention relates to have the micron particle or the nanoparticle of nitride coatings.In another typical embodiment, the present invention relates to have the micron particle or the nanoparticle of carbide coating.
The invention still further relates to micron particle and nanoparticle with the coating that forms through the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working.
The invention still further relates to surface treated micron particle and nanoparticle, wherein realize surface treatment through the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working.
The invention still further relates to works under normal atmosphere or rough vacuum condition is used for micron and/or nanoparticle are carried out surface-treated dielectric barrier discharge torch.In one embodiment, the present invention relates under normal atmosphere or rough vacuum condition, the work dielectric barrier discharge torch of the surface chemical property that is used to change micron and/or nanoparticle.In one embodiment, the present invention relates under normal atmosphere or rough vacuum condition, work and be used for applying the dielectric barrier discharge torch of micron and/or nanoparticle with organic coating.In one embodiment, the present invention relates under normal atmosphere or rough vacuum condition, work and be used for applying the dielectric barrier discharge torch of micron and/or nanoparticle with inorganic coating.In one embodiment, the present invention relates under normal atmosphere or rough vacuum condition, work and be used for applying the dielectric barrier discharge torch of micron and/or nanoparticle with metallic coating.In one embodiment, the present invention relates under normal atmosphere or rough vacuum condition, work and be used to produce the micron and/or the dielectric barrier discharge torch of nanoparticle with oxidized surface.
At last, in one embodiment, the present invention relates to the dielectric barrier discharge torch and powder particle is carried out the surface-treated purposes awing.
Through reading subsequently to the non-limitative illustration of exemplary, aforementioned and other purpose, advantage and characteristic of the present invention will be more obvious, and said embodiment only provides with reference to the form of accompanying drawing with embodiment.
Description of drawings
In the accompanying drawings:
Fig. 1 (a-j) illustrates according to the present invention the block diagram that micron particle and nanoparticle are carried out the various configurations of surface treatment and/or coating.
Fig. 2 (a-d) illustrates according to the present invention and to produce the various electrodes configurations that are used for micron particle and nanoparticle are carried out the dielectric barrier discharge of surface treatment and/or coating: (a) coaxal electrode disposes; (b) coaxial electrode configuration; (c) shell electrode configuration; And (d) staggered (multiple-staggered) electrode configuration of multichannel.
Fig. 3 illustrates: (a) comprise the photo of the dielectric barrier discharge torch assembly that the coaxal electrode configuration is in running order according to embodiment of the present invention, have the micron particle or the nanoparticle of oxide skin or organic coating in order to production; (b) according to the schematic cross-sectional front view of dielectric barrier discharge torch assembly of the present invention; Reach (c) the schematic cross-sectional front view of torch head, show central powder or finish materials precursor and inject probe and high voltage terminal and ground-electrode.
Fig. 4 illustrates: the photo that (a) comprises the dielectric barrier discharge torch assembly that the staggered shell electrode configuration of multichannel is in running order according to embodiment of the present invention; (b) comprise the diagram of the dielectric barrier discharge torch assembly of the staggered shell electrode configuration of water-cooled multichannel according to embodiment of the present invention; Reach the schematic cross-sectional front view of the dielectric barrier discharge torch assembly that (c) comprises the staggered shell electrode configuration of water-cooled multichannel, show each inlet and water-cooling channel.
Fig. 5 illustrates the schematic cross-sectional front view that comprises the dielectric barrier discharge torch assembly of multichannel water-cooled shell electrode according to embodiment of the present invention.This assembly comprises upstream zone and downstream section, and said upstream zone comprises through configuration makes micron particle or the charged pair of modules of nanoparticle, and said downstream section comprises a series of modules that charged micron particle or nanoparticle applied through configuration.
Fig. 6 (a-c) illustrates powder transmission electron microscope (TEM) Photomicrograph of nano-silicon dioxide particle.
Fig. 7 (a-c) illustrates transmission electron microscope (TEM) Photomicrograph of the polyethylene coated nano-silicon dioxide particle of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention, and the basic polyethylene coating uniformly of thick about 10nm is shown.
Fig. 8 (a-b) illustrates transmission electron microscope (TEM) Photomicrograph of the TR 301 coated with nano silicon dioxide granule of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention, and the basic TR 301 coating uniformly of thick about 5nm is shown.
Fig. 9 (a-b) illustrates transmission electron microscope (TEM) Photomicrograph of the polyhutadiene coated with nano silicon dioxide granule of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention, and the basic polyhutadiene coating uniformly of thick about 5nm is shown.
Figure 10 (a-c) illustrates sem (SEM) Photomicrograph of big aluminum metal particle.
Figure 11 (a-c) illustrates type of the having silicon-dioxide (SiO of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention xC yH z) sem (SEM) Photomicrograph of big aluminum particulate of coating (tetraethoxy-silicane is a coating precursor), and basic type silica dioxide coating uniformly is shown.
Figure 12 (a-b) illustrates field emission electron torch (FEG) the microscope Photomicrograph of nano aluminum particle.
Figure 13 (a-b) illustrates type of the having silicon-dioxide (SiO of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention xC yH z) field emission electron torch (FEG) the microscope Photomicrograph of nano aluminum particle of coating (the diethyl-dimethyl siloxanes is a coating precursor), and basic type silica dioxide coating uniformly is shown.
Figure 14 (a-b) illustrates transmission electron microscope (TEM) Photomicrograph of nano alumina particles.
Figure 15 (a-b) illustrates type of the having silicon-dioxide (SiO of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention xC yH z) transmission electron microscope (TEM) Photomicrograph of nano alumina particles of coating (the diethyl-dimethyl siloxanes is a coating precursor), and basic type silica dioxide coating uniformly is shown.
Figure 16 (a-c) illustrates field emission electron torch (FEG) the microscope Photomicrograph of nano barium phthalate particle.
What Figure 17 (a-c) illustrated the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention has a dysprosium oxide (Dy 2O 3) field emission electron torch (FEG) the microscope Photomicrograph of nano barium phthalate particle of inorganic coating, and basic dysprosium oxide coating uniformly is shown.
Figure 18 (a-c) illustrates sem (SEM) Photomicrograph of the big metallics of magnetic.
Figure 19 (a-c) illustrates sem (SEM) Photomicrograph of the big metallics of magnetic of type of the having iron coating (ferrocene is coating precursor) of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention, and basic type iron coating uniformly is shown.
Figure 20 illustrates sem (SEM) Photomicrograph of the big metallics of magnetic of type of the having cobalt coating (dicyclopentadienylcobalt is coating precursor) of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention, and basic type cobalt coating uniformly is shown.
Figure 21 illustrates energy dispersion spectrum (EDS) figure of the magnetic particle of cobalt coating, shows cobalt coating (blueness) and magnetic particle (grey).
Figure 22 (a-b) illustrates sem (SEM) Photomicrograph of big aluminum particulate.
Figure 23 (a-b) illustrates sem (SEM) Photomicrograph of the big aluminum particulate with polyacetylene coating (acetylene is coating precursor) of the dielectric barrier discharge torch assembly preparation of using embodiment of the present invention.
Figure 24 illustrates energy dispersion spectrum (EDS) figure of the big aluminum particulate of polyacetylene coating, shows aluminum particulate (redness) and polyacetylene coating (white green).
Figure 25 illustrates thermogravimetric analysis (TGA) figure, illustrates aluminum particulate that high density polyethylene(HDPE) applies under argon atmospher, from about 100 ℃ of mass losses to about 800 ℃ TR, when heating up with the speed of 10 ℃/min; The amount of the polymeric coating that is equivalent to basically to increase in the coating procedure in the mass loss below 550 ℃; The weight increase that observes at higher temperature is equivalent to the accumulation of oxide skin.
Figure 26 illustrates thermogravimetric analysis (TGA) figure, illustrates silicon dioxide granule that Vilaterm (a), polyhutadiene (b) and TR 301 (c) apply under air atmosphere, from about 100 ℃ of extremely mass losses in about 600 ℃ TR; The amount of the polymeric coating that this mass loss is equivalent to increase in the coating procedure basically; The weight increase that observes at higher temperature is equivalent to the accumulation of oxide skin.
Embodiment
In order to know and as one man to understand the term that uses in this specification sheets, provide a plurality of definition below.And, only if in addition definition, all scientific and technical terminologies that this paper uses have with the present invention under the identical implication of those of ordinary skill institute common sense of technical field.
" comprise " word " " or " a kind of " who uses with term in claims and/or the specification sheets; Can represent " one or a kind of ", but also can be consistent with the implication of " one or more or one or more ", " at least one or at least a ", " one or more or one or more ".Similarly, word " another or another kind " can be represented two or more perhaps at least two kinds or more kinds of at least.
As used in this specification sheets and claims; Word " comprises " (and arbitrary form); " have " (and arbitrary form), " comprising " (and arbitrary form) perhaps " contains " (and arbitrary form); Be non-limiting or open, and do not get rid of extra, NM key element or operation.
Term " about " comprises that in order to show numerical value measuring utensil or the method inherent error that this numerical value adopted changes.
The term that uses in this specification sheets " normal atmosphere or rough vacuum condition " is meant the pressure from about 5 normal atmosphere down to about 50Torr.
Used like this specification sheets, term " lower frequency " is meant 1MHz or littler frequency.
Used like this specification sheets, term " surface treatment " is meant the process that process that particle surface and gaseous environment (being plasma discharge) act on mutually or coating material are deposited on particle surface.Coating material comprises the chemical ingredients that is different from particle usually.Particle surface comprises oxidising process with the limiting examples of the process that gaseous environment acts on mutually.This process causes the formation of oxide skin usually.Particle surface causes usually that with the process that gaseous environment acts on mutually Surface Physical and chemical property change.The limiting examples of the effect of " surface treatment " comprises the oxidation-resistance and/or the fire resistance (being surface passivation) of increase, the wetting ability of change and hydrophobicity, and the powders that reduces tendency.
Used like this specification sheets, term " metal " is meant that all comprise the material of metal.This includes but not limited to pure metal, metalloid, metal alloy and conspicuous to those skilled in the art similar combination.
Used like this specification sheets, term " coating " is meant all types of coatings.This includes but not limited to porous coating (for example comprising uncoated space) and non-porous coating.In non-porous coating, coating is coated on the whole surface of particle usually with totally continuous mode, thereby does not expose the original surface of particle.In porous coating, the surface of particle part at least is coated.
In this manual, term " basically identical " is " even basically " commutative use perhaps, when being used to describe coating, does not almost have significant localized variation in the expression coating.
The present invention relates to powder particle carried out the surface-treated method by means of the dielectric barrier discharge torch of under normal atmosphere or rough vacuum condition, working.In embodiments of the invention, powder particle comprises micro polymer rice corpuscles and nanoparticle, metal micron particle and nanoparticle or their combination.In another embodiment of the present invention, powder particle comprises MOX micron particle and nanoparticle.Surface treatment causes that the surface chemical property of micron particle and nanoparticle changes, and perhaps produces to have thickness less than the coated particle of about 1nm to the coating of about 50nm.In embodiments of the invention, coating comprises polymer materials.In another embodiment of the present invention, coating comprises metallic coating, oxide coatings, nitride coatings or carbide coating.Other coating, type of being not limited to silica dioxide coating is known and in those skilled in the art's limit of power in the art.
The characteristic feature of dielectric barrier discharge is to exist at least one dielectric barrier (being isolator) and the discharge space between pair of electrodes.In addition, before having described dielectric barrier discharge can make chemical bond rupture, excited atom and branch subclass material and produce active substance such as radical.Within the scope of the invention, the limiting examples of active substance comprises atom such as He, Ar and the Ne that is in electronic ground state or excited state; Be in the molecule such as the N of electronic ground state or excited state 2, N for example 2, N 2 *, N 2 +And molecular fragment such as CH 3, CH 2, CH, NH 2, and NH.Other active substance is well known in the art and in those skilled in the art's limit of power.Dielectric barrier discharge can present the various forms (14,15) from floral designs (being jet pattern) to rule and apparent uniform pattern.
The dielectric barrier discharge torch is divided into non-heat (being non-equilibrium system) plasma system or cold plasma system.Thermal plasma has identical electronics of temperature and heavy particle (being that they are in thermal equilibrium each other).Yet the characteristic feature of Athermal plasma is to comprise temperature ion and the neutral substance (heavy particle) lower than electronics.Because heavy particle keeps lower temperature in plasma body, has avoided any unnecessary polymer unwinds, so the dielectric barrier discharge torch is described to be applicable to polymerization and depositing operation.The dielectric barrier discharge torch is that than the intrinsic advantage of other conventional thermal plasma torch the Athermal plasma state is set up easily under normal atmosphere or the situation near normal atmosphere (being normal atmosphere or rough vacuum condition).More than the normal atmosphere or near working under the atmospheric condition further advantage is being provided also, is promptly need not any costliness and be difficult to keep the equipment of vacuum, especially true when in dust atmosphere, working.
The representative instance that relates to the industrial application of dielectric barrier discharge technology comprises ozonizer and plasma display panel (15-17).Operating frequency is extremely counted GHz from line frequency usually, more typically from 1kHz to 500kHz.
Dielectric barrier discharge torch of the present invention is worked under normal atmosphere or rough vacuum condition, and is easily integrated in the powder production technology.According to embodiment of the present invention, (for example cause discharge in the annular space of Fig. 2 between a) at two concentric cylindrical quartz (being fused silica, silica glass) or vitrified pipe.According to embodiment of the present invention, between a pair of coaxial sleeve electrode that is arranged in cylindrical dielectric pipe (for example silica tube or vitrified pipe) surface, cause discharge.According to another embodiment of the present invention, cause discharge in cylindrical quartz between a pair of half-cylindrical shell electrode or the vitrified pipe.Vitrified pipe is especially effective dielectric barrier.According to another embodiment of the present invention, between two parallel quartz (being fused silica, silica glass) plate or ceramic plate, cause discharge.Other discharge configuration is within those skilled in the art's limit of power.
According to the particular case of dielectric barrier discharge torch assembly, electrode can be a water-cooled.Water cooled electrode is generally used for producing the micron particle with organic coating or the dielectric barrier discharge torch assembly of nanoparticle.Water cooled electrode guarantees good discharge cooling and test reproducibility usually.
According to embodiment of the present invention; The external ground electrode generally includes metal sheet or tinsel, wire cloth or metallic paint (for example platinum), and said metallic paint is coated on the outside surface of outer quartz or vitrified pipe (under the situation of arranged coaxial) and at least 700 ℃ temperature calcination.According to another embodiment of the present invention; The external ground electrode generally includes metal sheet or tinsel, wire cloth or metallic paint (for example platinum), and said metallic paint is coated on the outside surface of parallel vitreous silica plate or ceramic plate (under the situation of configured in parallel) and at least 700 ℃ temperature calcination.Use wire cloth that the advantage of the transparency can be provided, but the perhaps extra discharge of introducing between silk screen and the parallel plate between silk screen and outer quartz or vitrified pipe (under the situation of arranged coaxial) sometimes.Use metallic paint (for example platinum) can avoid this extra discharge and provide more uniformly discharging.Metallic paint can be painted various patterns, and its limiting examples comprises continuous pattern, helical pattern or circular pattern.Other pattern is within those skilled in the art's limit of power.According to embodiment of the present invention, metallic paint is platinum coating.Other metallic paint is not limited to electrically conducting coating such as gold or silver coating, all is well known in the art and in those skilled in the art's limit of power.Apply a kind of specific metallic paint pattern or multiple pattern, the track of may command powder, the also charged and coating of may command powder.
Should think that the powder particle of process plasma slab has the identical electric charge of symbol.Powder particle thereby repulsion are each other smashed already present aggregate and are avoided forming new aggregate.Through smashing and avoid the formation of aggregate, realize more effectively and more uniform particle coated.Solids through plasma slab are often electronegative, because electronics is with the speed bump particle surface more much higher than the ion of positively charged.Dielectric barrier discharge torch of the present invention comprises a plurality of inlets that are used to introduce finish materials precursor (like monomer), guarantees that powder particle to be coated had the powders of reduction before the experience coating procedure.
According to embodiment of the present invention, the dielectric barrier discharge torch can the work of continuous discharge pattern.According to another embodiment of the present invention, the dielectric barrier discharge torch can the work of intermittent discharge pattern.When working, incessantly to the power supply of dielectric barrier discharge torch, to keep discharge with the continuous discharge pattern.When working, supply power to the dielectric barrier discharge torch with the intermittent discharge pattern with periodically (promptly connecting and cut off).Time lag between the igniting can be as short as about several milliseconds in succession, perhaps as selecting, also can extend to the several seconds.Each round-robin " cut-out " cycle needn't be identical with the time length in " connection " cycle, can be set to several milliseconds independently, also can extend to the several seconds." cut-out " and " connection " cycle can be distinguished and control independently.
Make dielectric barrier discharge torch of the present invention improve control through reducing energy loads to coating procedure with the work of intermittent discharge pattern.Than with the work of continuous discharge pattern, to work with the intermittent discharge pattern, energy loads can reduce by 10 times or more times.And when working with the intermittent discharge pattern, the severity of any potential injury that the UV radiation that plasma body sends causes is lower.
Can use dielectric barrier discharge torch of the present invention to deposit various polymeric coatings (like polymeric film).The limiting examples of the coating monomer that the present invention is contemplated to (being the finish materials precursor) comprises acetylene, ethene, isoprene, SWS-F 221 (HMDSO), tetraethoxysilane (TEOS), tetraethoxy-silicane, diethyl-dimethyl siloxanes, 1; 3-divinyl, vinylbenzene, TEB 3K, tetrafluoroethylene (TFE), methane, ethane, propane, butane, pentane, hexane, hexanaphthene, acetylene, ethene, propylene, benzene, isoprene, SWS-F 221, tetraethoxysilane, tetraethoxy-silicane, diethyl-dimethyl siloxanes, 1; 3-divinyl, vinylbenzene, TEB 3K, tetrafluoroethylene, pyrroles, hexanaphthene, 1-hexene, allyl amine, methyl ethyl diketone, oxyethane, SY-Monomer G, acetonitrile, THF, ETHYLE ACETATE, diacetyl oxide, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, triethoxy vinyl silanes, 1-octanol, vinylformic acid, ferrocene, dicyclopentadienylcobalt, cyclooctatetraene iron tricarbonyl, (methyl) (cyclopentadienyl moiety) (dicarbapentaborane) iron, (dicyclopentadienyl) (dicarbapentaborane) iron dipolymer, cyclopentadienyl moiety cobalt acetyl acetone cobalt, nickel acetylacetonate, dimethyl--(2,4-pentane-diketone closes) gold (III), nickle carbonoxide, iron carbonyl, acetyl acetone tin, acetyl acetone indium and tetramethyl-hexanedione close indium.Should be understood that, in scope of the present invention and those skilled in the art's limit of power, also can use other monomer.In addition, should be understood that the thickness of polymeric coating and molecular weight can change, and the parameter of the thickness of controlling polymers coating and molecular weight is within those skilled in the art's limit of power.According to embodiment of the present invention, coating is an organic coating.According to another embodiment of the present invention, coating is an inorganic coating.The limiting examples of inorganic coating precursor comprises pure metal, oxide compound, nitride, carbide or its combination.
Can use dielectric barrier discharge torch of the present invention to apply size range from nano level to micron-sized various particles.Polymeric coating (being polymeric film) can deposit through gaseous state, liquid state or solid precursor.The limiting examples of gaseous precursors comprises acetylene, ethene and divinyl.The limiting examples of liquid precursor comprises isoprene, Virahol dysprosium, tetraethoxysilane (TEOS), diethyl-dimethyl siloxanes (DEDMS), SWS-F 221 (HMDSO), TEB 3K (MMA) and pyrroles.The limiting examples that is used for the solid precursor of metal refining coating comprises ferrocene and dicyclopentadienylcobalt.
Fig. 1 (a-j) shows and uses dielectric barrier discharge torch of the present invention to prepare the block diagram of the various configurations of surface treated micron particle and nanoparticle.Shown in summarys, this method comprises powder feed step, charging and surface treatment step, reaches the collection step like institute among the figure.Can use conventional powder feeder that powder (i.e. micron and/or nanoparticle) is sent into the dielectric barrier discharge torch.Should be understood that, also can use other feeding unit that is suitable for dusty raw materials is delivered to plasma torch, and within those skilled in the art's limit of power.In embodiments of the invention, can powder be sent into the dielectric barrier discharge torch by means of the atomizing probe.In this embodiment, raw material comprises the liquid that contains dispersed powders.
Can dusty raw materials directly be sent into main discharge district (Fig. 1 a, Fig. 1 c, Fig. 1 d and Fig. 1 e) with forming isoionic gas through one or more inlets, perhaps, send into twilight sunset district, downstream (Fig. 1 i) as selecting.In embodiments of the invention, one or more inlets are arranged in the central quartzy injection tube of dielectric barrier discharge torch.In another embodiment; Can dusty raw materials be sent into dielectric barrier discharge torch (Fig. 1 b in the mid-way; Fig. 1 f and Fig. 1 g), perhaps, arrange between the continuum barrier discharge torch of operating in front and back dusty raw materials is sent into dielectric barrier discharge torch (Fig. 1 h) as selecting.In an embodiment more of the present invention, the solution that comprises powder stock can be sent into dielectric barrier discharge torch (Fig. 1 j) through the atomizing probe.The solution that comprises powder stock can be chosen wantonly and also comprise the finish materials precursor.
In embodiments of the invention, can monomer or coating material precursor be injected main discharge district (Fig. 1 c) with the gas and the dusty raw materials that form plasma body.In another embodiment of the present invention, can monomer or coating material precursor be injected main discharge district (Fig. 1 i) with the gas that forms plasma body.In another embodiment of the present invention, can be in the mid-way with monomer or coating material precursor with dusty raw materials injected media barrier discharge torch (Fig. 1 f).In another embodiment of the present invention; Can be independent of dusty raw materials in the mid-way separately with monomer or coating material precursor injected media barrier discharge torch (Fig. 1 d and Fig. 1 g), perhaps arrange injected media barrier discharge torch (Fig. 1 e and Fig. 1 h) between the continuum barrier discharge torch of work in front and back.
Monomer or coating material precursor can be gas, steam or liquid form.In embodiments of the invention, make powder in the dielectric barrier discharge torch, carry out surface treatment process after charged.In embodiments of the invention, in downstream twilight sunset district, carry out surface treatment process (Fig. 1 i).Surface treated powder is collected in conventional powder catcher at last or is suitable for collecting any other device of powder.
Fig. 2 shows the multiple electrode configuration that is used for micron particle and nanoparticle are carried out the dielectric barrier discharge of surface treatment and/or coating formed according to the present invention.Fig. 2 a shows the dielectric barrier discharge torch 10 with coaxal electrode configuration.Pair of electrodes is separated by two concentric quartz tubes or vitrified pipe 16.Contre electrode 12 links to each other with high-voltage power supply usually, and outer electrode 14 common ground connection.The gas that forms plasma body is injected the annular region 18 that limits a pair of concentric cylindrical silica tube or vitrified pipe 16.The plasma discharge that adopts the coaxal electrode configuration to produce has annular shape usually.Fig. 2 b shows the dielectric barrier discharge torch 20 with coaxial electrode configuration.Electrode pair comprises that cylindrical conductor and coaxial arrangement are in the outside surface of silica tube or vitrified pipe 26.One of electrode 22 links to each other with high-voltage power supply usually, and another electrode 24 common ground connection.Inject the right cylinder 28 that limits silica tube or vitrified pipe 26 with forming isoionic gas.The plasma discharge that adopts the coaxial electrode configuration to produce will be full of the right cylinder of silica tube or vitrified pipe 26.Fig. 2 c shows the dielectric barrier discharge torch 30 with core-shell electrode configuration.Shell electrode 32 comprises a pair of half-cylindrical electrode 34 and 36.In embodiments of the invention, half-cylindrical electrode comprises the pair of metal plate of the outside surface that is arranged in silica tube or vitrified pipe 36.Should be understood that, also can use other conductive electrode material within the scope of the invention, and within those skilled in the art's limit of power.One of half-cylindrical electrode 34 links to each other with high-voltage power supply usually, and another half-cylindrical electrode 36 common ground connection.Inject the right cylinder 39 that limits silica tube or vitrified pipe 36 with forming isoionic gas.Should be understood that, can many double cylindrical electrodes be arranged in the outside surface of silica tube or vitrified pipe 36.Fig. 2 d shows the dielectric barrier discharge torch 40 with many core-shell electrode configurations.Dielectric barrier discharge torch 40 comprises the core-shell electrode 42 and 44 of two pairs of interlaced configurations.In embodiments of the invention, half-cylindrical electrode comprises the pair of metal plate of the outside surface that is arranged in silica tube or vitrified pipe 49.Should be understood that, also can use other conductive electrode material within the scope of the invention, and within those skilled in the art's limit of power.In embodiments of the invention, half-cylindrical electrode pair 42 and 44 90 ° interlaced with each other.Should be understood that, also can adopt other stagger angle within the scope of the invention, and within those skilled in the art's limit of power.Half-cylindrical electrode 41 links to each other with high-voltage power supply with 45 usually, and half-cylindrical electrode 43 and 46 common ground connection.Inject the right cylinder 48 that limits silica tube or vitrified pipe 49 with forming isoionic gas.Core-shell electrode between 90 ° stagger angle, plasma distribution more uniformly can be provided in the cylindrical cavity of silica tube or vitrified pipe.According to the rated output of discharge, the configuration of the electrode of Fig. 2 can be water-cooled or gas cooling.
Fig. 3 b is the schematic cross-sectional front view according to dielectric barrier discharge torch assembly 50 of the present invention.Assembly 50 comprises central body portion, and this central body portion comprises the outer quartz tube 52 that wherein is provided with at least one ground-electrode 54 and high voltage terminal 56.On high voltage terminal, apply the High Level AC Voltage of frequency usually for about 20kHz.In embodiments of the invention, the voltage that is applied is generally about 5～15kV.The assembly of Fig. 3 b is generally used for preparing micron particle or the nanoparticle with oxide skin or organic coating.In embodiments of the invention, high voltage terminal 56 can be a water-cooled.The space that annular discharge gap 57 limits between at least one ground-electrode 54 and the high voltage terminal 56.In annular discharge gap (being the space between one or more ground-electrodes and the high voltage terminal), cause discharge.In embodiments of the invention, discharging gap can be by the space boundary between space between the intravital a pair of silica tube of torch or the parallel quartz plate.Center injection tube 58 extends in high voltage terminal 56 basically coaxially.In embodiments of the invention, injection tube 58 configurable one-tenth in center have adjustable length.Dielectric barrier discharge torch assembly 50 also comprises the torch body 59 of center injection tube 58 from wherein passing; This torch body operationally is fixed in the upper end of silica tube 52, and comprises a plurality of opening 60, water-in and water outlet (promptly under the situation of water-cooled high voltage terminal) and ground connection and high pressure connections that are used to receive plasma gas raw material (optional sheath layer gas raw material (sheath gas feed)).
Choose wantonly and comprise that the powder collection chamber 62 of one or more tangentials inlet 64 is arranged at the lower end of silica tube 52, is used to receive surface treated powder.In embodiments of the invention, powder collection chamber 62 is installed on the lower end of silica tube 52 coaxially, is located substantially on the exit of plasma discharge.Can pass through one or more tangentials inlet 64 injecting inert gass or reactive gas, control the atmosphere in discharge exit (promptly being right after the zone of powder collection chamber 62 tops).
In embodiments of the invention, the dielectric barrier discharge torch comprises removable silica tube or vitrified pipe, so that different discharging gap configurations to be provided.Can form radial width and be the discharging gap of about 1mm to about 10mm.Bigger discharging gap is within those skilled in the art's limit of power.The length of discharge depends on the length (concentric and shell mould configuration) of external ground electrode.For arranged coaxial, the length of discharge depends on the length of high voltage terminal, ground-electrode and gap therebetween.For the configuration of multichannel shell electrode, the length of discharge depends on the length of core-shell electrode and gap therebetween.In another embodiment of the present invention, the dielectric barrier discharge torch comprises the pair of parallel quartz plate (being concentric arrangement) that is separated for the gap of about 1mm to 10mm by width.Gap width bigger between the parallel plate is within those skilled in the art's limit of power.
According to embodiment of the present invention, the external ground electrode generally includes metal sheet or tinsel, wire cloth or the metallic paint (for example platinum) that puts on outer quartz tube or vitrified pipe (for example arranged coaxial) outside surface.Metallic paint can apply into different patterns and shape, and its limiting examples comprises continuous pattern, helical pattern or circular pattern.
With reference to Fig. 3 b; The center injection tube 58 that almost coaxial extends in high voltage terminal 56 can have adjustable height, so that the position-controllable of dusty raw materials and/or monomer injected media barrier discharge torch (promptly directly inject the main discharge district with main air stream or inject in a certain mid-way or inject in the outlet of discharging gap).In embodiments of the invention, the dielectric barrier discharge torch comprises the outer tube 52 that discharge outlet and air are separated.This configuration allows to introduce extra gas, normally rare gas.
Fig. 3 c shows the exemplary of cooling loop of the high voltage terminal of dielectric barrier discharge torch 70.In this specific embodiments, cooling system is sealed in the stainless steel cylinder 71 fully, and this stainless steel cylinder is positioned at the inner quartz tube 72 of dielectric barrier discharge torch 70.Water-in and water outlet are respectively with numeral 74 and 76 expressions.High voltage terminal and ground-electrode are respectively with numeral 77 and 78 expressions.The pair of outer coaxial quartz tube is with numeral 79 and 80 expressions.Intermediary silica tube 79 serves as dielectric medium.Outer quartz tube 80 will discharge and air insulated.This cooling configuration guarantees fully to cool off high voltage terminal and discharging gap, thereby can apply high voltage electric and can not reach typical higher ion temperature (cold plasma).In embodiments of the invention, cooling system carries out work with water as quench liquid.In another embodiment of the present invention, cooling system comprises the closed system of carrying out work with deionized water as quench liquid.Other quench liquid (being synthetic oil or polyvalent alcohol) is known in the art and in those skilled in the art's limit of power.Through with the quench liquid of synthetic oil, can realize higher plasma discharge temperature as high voltage terminal.Higher plasma discharge temperature allows use to need the raw material monomer (being the coating material precursor) of higher vaporization temperature to carry out the polymer-coated of powder, avoids raw material monomer condensation in injection tube simultaneously.
Fig. 4 (a-b) shows the common exemplary that is used to prepare the dielectric barrier discharge torch assembly of the organic coating on metal and/or MOX micron particle or the nanoparticle through configuration.This configuration also can be used for preparing inorganic coating.This dielectric barrier discharge torch comprises the cooling system that seals fully and be arranged in the double-walled silica tube.
Fig. 4 c is the schematic cross-sectional front view that has the dielectric barrier discharge torch assembly 90 of the staggered shell electrode configuration of water-cooled multichannel according to an embodiment of the present invention.Dielectric barrier discharge torch assembly 90 comprises upper reaches module 92, and this upper reaches module comprises concentric quartz tubes 94 and 96.One of electrode links to each other with high-voltage power supply, another electrode grounding.To form isoionic gas via inlet 98 and introduce discharge cavity.Produce plasma body in the silica tube 96 between a pair of half-cylindrical electrode, said half-cylindrical electrode constitutes the first shell electrode and is arranged on the surface of silica tube 96.Section 100 limits the gap of separating upper reaches module 92 and downstream module 102.Downstream module 102 comprise the structure identical with the first shell electrode but with another interconnected shell electrode of the first shell electrode.Plasma body enters the chamber 104 that is positioned at module 102 downstream.Chamber 104 comprises the inlet 106 that is used to introduce powder delivery gas.Delivering gas guarantees that the particle product is delivered to the collection module through port one 08.Two modules 92 and 102 are provided with the water-cooling channel (not shown), and said water-cooling channel is arranged in the annular space between concentric quartz tubes 94 and 96.Water is introduced via inlet 112 and is discharged via port one 10.Can micron and/or nanoparticle be sent into dielectric barrier discharge torch assembly 90 with the gas of formation plasma body through inlet 98.Can finish materials be sent into dielectric barrier discharge torch assembly 90 through the port one 14 that is arranged between module 92 and 102.Inlet 110 allows to introduce additional plasma gas or wall sheath layer gas (wall sheath gas).Should be understood that under the situation that does not break away from design of the present invention and essence, can improve dielectric barrier discharge torch assembly 90, this improvement is within those skilled in the art's limit of power.
Fig. 5 shows the schematic cross-sectional front view of the dielectric barrier discharge torch assembly 120 that has the staggered shell electrode configuration of water-cooled multichannel (five road shell electrode modules) according to an embodiment of the present invention.Dielectric barrier discharge torch assembly 120 comprises upstream zone 122, and this upstream zone comprises a pair of shell electrode module 124.Shell electrode 128 is arranged in the surface of silica tube or vitrified pipe 126.Shell electrode module 124 is surrounded by polymer matrix composite 130, and shell electrode 128 embeds in the said matrix material.Shell electrode module 124 is provided with the water-cooling channel (not shown).Water is introduced via inlet 132 and is discharged via port one 34.Inlet 136 allows to introduce sheath layer gas at the inside circumference of silica tube or vitrified pipe 126 inwalls.The gas that will form plasma body through inlet 138 is introduced discharge cavity.Can micron and/or nanoparticle be sent into dielectric barrier discharge torch assembly 120 with the gas of formation plasma body through inlet 138.Dielectric barrier discharge torch assembly 120 also comprises downstream section 140, this downstream section comprise structure identical with first pair of shell electrode module 124 but with three groups of interconnected shell electrode modules 142 of first pair of shell electrode module 124.Shell electrode 142 is arranged in the surface of silica tube or vitrified pipe 126 and is provided with the water-cooling channel (not shown).Water is introduced through inlet 144 and is discharged through port one 46.Inlet 148 allows to introduce other sheath layer gas at the inside circumference of silica tube or vitrified pipe 126 inwalls.Plasma discharge gets into through outlet 150 and collects the module (not shown).Adopt the configuration of multichannel shell electrode module that technological flexibility can be provided, because can increase or reduce the number of module according to processing requirement.In embodiments of the invention, upstream zone 122 can be specifically designed to and make pending surface-treated micron and/or nanoparticle charged, and downstream section 140 can be specifically designed to and carries out surface treatment.Heating tube can be arranged in the upstream position of section 122 with the control powder temperature, because heat is the regulation and control parameter of particle charging.In another embodiment of the present invention, the two all can be used for the surface treatment of micron and/or nanoparticle raw material upstream zone 122 and downstream section 140.Back one embodiment allows to increase the frequency of exposure of pellet feed and plasma discharge.
Embodiment
Some embodiment below are provided, are used to explain the efficient of dielectric barrier discharge torch of the present invention when micron and/or nanoparticle are carried out plasma surface treatment.
Power supply
In one embodiment, the power supply that uses of dielectric barrier discharge torch of the present invention is the corona unit (Polydyene 1 corona unit) of 3DTSOFTAL.The main characteristic of this power supply is summarized in the following table 1.
Table 1: power supply characteristic
Power (W) 500 (peaks)
Voltage (kV) 15
High pressure adjustment (kV) 5-15
Frequency (kHz) ～20-25
The intermittent mode treatment time (s) 0.2-25
Working conditions
The working conditions of dielectric barrier discharge torch of the present invention can change according to powder properties, required surface treatment, required coating and finish materials (being monomer).The residence time that control surface is handled material is that the control thickness that applies institute is requisite.Representational working conditions is summarized in the following table 2.
Table 2: working parameter
Figure G2007800366020D00171
Figure G2007800366020D00181
*The residence time of powder is about 1 second.
Use Tekronix digital indicator (TEK TDS 1002-TDS2MEM) and Tekronix high-voltage probe (75MHz, 40kV) monitoring voltage and electric current.Electric current is carried out integration,, then utilize this Lissajou's figure to confirm discharge power (15-18) to show the Lissajou's figure (Lissajous figure) of voltage charging.The representative electrology characteristic of discharge is summarized in the following table 3.
Table 3: discharge characteristic
Sample # Power (W) Gas temperature (T in the discharging gap g(℃))
060310-02 80 225
060315-01 139 360
The coating result of metal and metal oxide powder
Sem (SEM) Photomicrograph through coating powders (Figure 10,11,18-20,22 and 23) is provided.Also provide through the physical property of coating powders such as the specific surface area of powder (utilizing " BraunerEmmett Teller " (BET) method measurement).To the carbon amount of powder surface increase in the coating procedure, with result's tabulation of x-ray photoelectron spectroscopy (XPS).This analytical procedure provides accurate quantitative analysis (atom composition) for the concentration (%) of the element of existence.And, show energy dispersion spectrum (EDS) spectrogram result, the information of relevant coating in the position of powder surface (Figure 21 and 24) is provided.At last, thermogravimetric analysis (TGA) result is shown, quantitative information (Figure 25 and 26) is provided to the amount that is deposited on the coating (being polymkeric substance) on the powder.
For the silica nanometer powder, tested the specific surface area (BET) before and after applying, the result is shown in following table 4.The noticeable change of specific surface area shows clearly, and significant disaggregation has taken place in coating procedure.
Table 4: silicon-dioxide and through the specific surface area result of coating silicon dioxide nanoparticle
Sample # BET(m 2/g)
Original silica nanometer powder 120.9
060613-01 227.3
060613-02 175.1
060613-03 170.5
Listed x-ray photoelectron spectroscopy (XPS) result of aluminium powder before and after applying in the following table 5 and 6.Bound energy Eb depends on the atom oxidation state and the chemical bond on every side of electronic migration.Only detect on nearly surface the electronics that (degree of depth or littler) at the most produces.The slow sweep of carbon atom provides the information of relevant its bond type.
Table 5: aluminum oxide and through the XPS result of coating alumina powder
Figure G2007800366020D00192
Table 6: the XPS result of relevant carbon atom bond type
Photopeak Peak position (eV) Explanation
C1s 285 C-H/C-C
C1s 286.3-286.7 C-O
C1s 287.8-288.2 C＝O
With regard to aluminium powder, TGA analyzes that the loss of phaneroplasm amount is no more than 0.5%, and this shows the existence of film.The localized heat cracking of the aluminium powder that a small amount of high density polyethylene(HDPE) applies in the time of about 300 ℃ causes continuous weightlessness.Weightlessness is corresponding to the complete pyrolysis of high density polyethylene(HDPE) chain in the time of about 370 to about 500 ℃.The oxidation of the weightening finish indication aluminium powder that when higher temperature, observes.The typical TGA graphic representation of the aluminium powder of high density polyethylene(HDPE) coating has been shown among Figure 25.
Should be understood that application of the present invention is not limited to concrete structure and parts mentioned above.The present invention can have other embodiment and can implement in a different manner.In addition, should be understood that word used herein or term are illustrative and nonrestrictive.Therefore, although the present invention has been carried out as above explanation,, can improve the present invention not breaking away under the situation of liking design of the present invention, scope and essence that claim limits enclosed through exemplary.
Reference
1.He，W.；Guo，Z.；Pu，Y.；Yan，L.；and?Si，W.；Polymer?coating?on?the?surface?of?zirconiananoparticles?by?inductively?coupled?plasma?polymerization.Journal?of?Applied?Physics?Letters，2004，85(6)，896.
2.Shi，D.；Wang，S.X.；Van?Ooij，W.J.；Wang，L.M.；Zhao，J.；and?Yu，Z.；Uniform?depositionof?ultra-thin?polymer?films?on?the?surfaces?of?Al 2O 3?nanoparticles?by?a?plasma?treatment.Journalof?Applied?Physics?Letters，2001，78(9)，1243.
3.Shi，D.；Lian，J.；He，P.；Wang，L.M.；Van?Ooij，W.J.；Schulz，M.；Liu，Y.；and?Mast，D.B.；Plasma?deposition?of?ultra-thin?polymer?films?on?carbon?nanotubes.Applied?Physics?Letters，2002，81(27)，5216.
4.Schallehn，M.；Winterer，M.；Wirich，T.E.；Keiderling，U.；and?Hahn，H.；In?Situ?Preparationof?Polymer?Coated?Alumina?Nanopowders?by?Chemical?Vapor?Synthesis.Chemical?VaporDeposition，2003，Vol.9(1)，40.
5.Vollath，D.；and?Szabo，D.V.；Oxide-polymer?nanocomposites?as?new?luminescent?materials.Journal?of?Nanoparticle?Research，2004，6，181-191.
6.Vollath，D.and?Szabo，D.V.；Coated?nanoparticles：A?new?way?to?improved?nanocomposites.Journal?of?Nanoparticle?Research，1999，1，235.
7.Lik?Hang?Chau，J；Hsu，M.；Hsieh，C.；and?Kao，C.；Microwave?plasma?synthesis?of?silvernanopowders.Materials?Letters，2005，Vol?59，905.
8.Lik?Hang?Chau，J；Hsu，M.；Hsieh，C.；and?Kao，C.；Microwave?plasma?synthesis?of?Co?andSiC-coated?Co?nanopowders.Materials?Letters，2006，Vol?60，947.
9.Kouprine，A.；Gitzhofer，F.；Boulos，M.；and?Fridman，A.；Polymer?like?C：H?thin?filmcoating?of?nanopowders?in?capacitively?coupled?rf?discharge.Plasma?Chemistry?and?PlasmaProcessing，2004，24(2)，189.
10.Dumitrache，F.；Morjan，I.；Alexandrescu，R.；Morjan，R.E.；Voicu，I.；Sandu，I.；Soare，I.；Ploscaru，M.；Fleaca，C.；Ciupina，V.；Prodan，G.；Rand，B.；Brydson，R；and?Woodword，A.Nearly?monodispersed?carbon?coated?iron?nanoparticles?for?the?catalytic?growth?of?nanotubes/nanofibers.Diamond?and?Related?Materials，2004，13，362.
11.Ermoline，A.；Shoenitz，M.；Dreizein，E.；and?Yao，N.；Production?of?carbon?coatedaluminum?nanopowders?in?pulsed?microarc?discharge.Nanotechnology，2002，13，638.
12.Sawada，Y.；Kogoma，M.；Plasma?polymerized?tetrafluoroethelyne?coatings?on silicaparticles?by?atmosphe?ric?pressure?glow?discharge.Powder?Technology，1997，90，245.
13.Lei，H.；Tang，Y.；Li，J.；Luo，J.；and?Li，X.；In-Situ?Organic?Coating?of?Metal?Nanoparticles.Applied?Physics?Letter，2006，88.
14.Kogelschatz，U.；Filamentary，Patterned，and?Diffuse?Barrier?Discharges.；IEEE?Transactionson?Plasma?Science，2002，30(4)，1400.
15.Becker，K.H.；Kogelschatz，U.；Schoenbach，K.H.；and?Barker，R.J.Eds.，Non-Equilibrium?AirPlasmas?at?Atmospheric?Pressure，IOP?2004，Chapter?6，276-306.
16.Kogelschatz，U.；Dielectric-barrier?discharges：Their?history，discharge?physics，andindustrial?applications.Plasma?Chemistry?and?Plasma?Processing，2003，23(1)，1.
17.Kogelschatz，U.；and?Eliasson，B.Ozone?Generation?and?Applications.Handbook?ofElectrostatic?Processes：Chang，J.S.；Kelly?A.J.and?Crowley?J.M.Eds.(Marcel?Dekker，NewYork?1995)，581-605.
18.Manley，T.C.；The?electrical?characteristics?of?the?ozone?discharge.Trans.Electrochem.Soc.1943，84，83.
19.Bretagnol，F.；Tatoulian，M.；Khonsari，F.A.；Lorang，G.；and?Amouroux，J.；Surfacemodification?of?polyethylene?powder?by?nitrogen?and?ammonia?low?pressure?plasma?in?a?fluidizedbed?reactor.Reactive?and?functional?polymers，2004，61：p.221.
20.Leroy，J.B.；Fatah，N.；Mutel，B.and?Grimblot.J.Treatment?of?polyethylene?powder?using?aremote?nitrogen?plasma?reactor?coupled?with?a?fluidized?bed：influence?on?wettability?andflowability.Plasma?and?Polymers，2003，8(1)：p.13.

Claims (25)

1. one kind is carried out the surface-treated method to powder particle, comprising:
A) the granular powder material is sent into dielectric barrier discharge torch assembly, comprising upper reaches shell electrode and downstream shell electrode, each shell electrode comprises a pair of half-cylindrical shell electrode, and wherein said downstream shell electrode is arranged with interlaced configuration with respect to upper reaches shell electrode;
B) particle in the said dielectric barrier discharge torch assembly is carried out surface-treated awing, produce surface treated particle; And
C) collect said surface treated particle.
2. the process of claim 1 wherein that (b) comprises makes particle surface act on mutually with plasma discharge.
3. the process of claim 1 wherein that (b) comprising: generate coating material through the coating material precursor being injected said dielectric barrier discharge torch assembly; And said coating material is deposited on particle surface and produces the particle through applying.
4. the process of claim 1 wherein that powder particle is selected from: micron particle, nanoparticle and composition thereof.
5. the method for claim 4, wherein powder particle is selected from: polymer particle, metallics, metal oxide particle and composition thereof.
6. the method for claim 3 wherein has through the particle that applies and is selected from following coating: organism coating and inorganics coating.
7. the method for claim 3, wherein said coating material precursor comprises the monomer that stands plasma polymerization.
8. the method for claim 7; Wherein said monomer is selected from: acetylene, ethene, isoprene, SWS-F 221, tetraethoxysilane, diethyl-dimethyl siloxanes, 1; 3-divinyl, vinylbenzene, TEB 3K, tetrafluoroethylene, methane, ethane, propane, butane, pentane, hexane, hexanaphthene, propylene, benzene, pyrroles, 1-hexene, allyl amine, methyl ethyl diketone, oxyethane, SY-Monomer G, acetonitrile, THF, ETHYLE ACETATE, diacetyl oxide, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, triethoxy vinyl silanes, 1-octanol, vinylformic acid, ferrocene, dicyclopentadienylcobalt, cyclooctatetraene iron tricarbonyl, (methyl) (cyclopentadienyl moiety) (dicarbapentaborane) iron, (dicyclopentadienyl) (dicarbapentaborane) iron dipolymer, cyclopentadienyl moiety cobalt acetyl acetone cobalt, nickel acetylacetonate, dimethyl--(2,4-pentane-diketone closes) gold (III), nickle carbonoxide, iron carbonyl, acetyl acetone tin, acetyl acetone indium and tetramethyl-hexanedione close indium.
9. the method for claim 3, wherein said coated particle have and are selected from following coating: polymeric coating, metallic coating, oxide coatings, nitride coatings and carbide coating.
10. the process of claim 1 wherein that the wherein said dielectric barrier discharge torch of dielectric barrier discharge torch assembly assembly works under normal atmosphere or rough vacuum condition, wherein said normal atmosphere or rough vacuum condition are that how is the pressure of 5 normal atmosphere down to 50Torr.
11. the process of claim 1 wherein that said dielectric barrier discharge torch assembly is in intermittent mode work.
12. one kind is carried out surface-treated equipment to powder particle awing, this equipment comprises:
-dielectric barrier discharge torch, it comprises:
Be used for plasma gas is sent into first inlet of said torch;
Be used for the granular powder material is sent into second inlet of said torch; With
The discharge chamber that is used for the said granular powder material of surface treatment; This discharge chamber comprises electrode structure; Comprising upper reaches shell electrode and downstream shell electrode, each shell electrode comprises a pair of half-cylindrical shell electrode, and wherein said downstream shell electrode is arranged with interlaced configuration with respect to upper reaches shell electrode; And
The device of the surface treated particle of-collection;
Wherein through making the gas that forms plasma body produce plasma discharge through said discharge chamber; And wherein said plasma discharge is facilitated awing the surface-treated to particle.
13. the equipment of claim 12, wherein said surface treatment discharge chamber comprises the device that particle surface and plasma discharge are acted on mutually.
14. the equipment of claim 12 also comprises:
Be used for the coating material precursor is sent into the 3rd inlet of said dielectric barrier discharge torch;
Said coating material precursor provides coating material and said particle is coated.
15. the equipment of claim 12, wherein powder particle is selected from: micron particle, nanoparticle and composition thereof.
16. the equipment of claim 12, wherein said discharge chamber comprises dielectric tube.
17. the equipment of claim 16, wherein said dielectric tube comprises silica tube.
18. the equipment of claim 16, wherein said dielectric tube comprises vitrified pipe.
19. comprising, the equipment of claim 12, wherein said electrode structure is selected from following material: metal sheet, tinsel, wire cloth and metallic paint.
20. the equipment of claim 12, wherein said first inlet and said second inlet are the common inlets.
21. the equipment of claim 12, wherein said first inlet limits different feeds with said second inlet.
22. the dielectric barrier discharge torch that limits in the claim 12 carries out the surface-treated purposes to powder particle awing.
23. a surface treated particle, the dielectric barrier discharge torch preparation of said particle through limiting in the claim 12.
24. the equipment of claim 12, wherein said dielectric barrier discharge torch is worked under normal atmosphere or rough vacuum condition, and wherein said normal atmosphere or rough vacuum condition are that how is the pressure of 5 normal atmosphere down to 50Torr.
25. the equipment of claim 12, wherein said dielectric barrier discharge torch is in intermittent mode work.
CN2007800366020A 2006-07-31 2007-07-31 Plasma surface treatment using dielectric barrier discharges Expired - Fee Related CN101573467B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US83416606P 2006-07-31 2006-07-31
US60/834,166 2006-07-31
US83640306P 2006-08-09 2006-08-09
US60/836,403 2006-08-09
PCT/CA2007/001349 WO2008014607A1 (en) 2006-07-31 2007-07-31 Plasma surface treatment using dielectric barrier discharges

Publications (2)

Publication Number Publication Date
CN101573467A CN101573467A (en) 2009-11-04
CN101573467B true CN101573467B (en) 2012-11-28

Family

ID=38996824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800366020A Expired - Fee Related CN101573467B (en) 2006-07-31 2007-07-31 Plasma surface treatment using dielectric barrier discharges

Country Status (9)

Country Link
US (1) US8263178B2 (en)
EP (1) EP2052097B1 (en)
JP (1) JP5260515B2 (en)
KR (1) KR101428679B1 (en)
CN (1) CN101573467B (en)
CA (1) CA2659298C (en)
DE (1) DE07785015T1 (en)
RU (1) RU2462534C2 (en)
WO (1) WO2008014607A1 (en)

Families Citing this family (107)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9682425B2 (en) 2009-12-08 2017-06-20 Baker Hughes Incorporated Coated metallic powder and method of making the same
US8403037B2 (en) 2009-12-08 2013-03-26 Baker Hughes Incorporated Dissolvable tool and method
DE10260745A1 (en) * 2002-12-23 2004-07-01 Outokumpu Oyj Process and plant for the thermal treatment of granular solids
EP1938907A1 (en) * 2006-12-28 2008-07-02 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Deposition of particles on a substrate
US8748785B2 (en) * 2007-01-18 2014-06-10 Amastan Llc Microwave plasma apparatus and method for materials processing
US10039927B2 (en) 2007-04-23 2018-08-07 Plasmology4, Inc. Cold plasma treatment devices and associated methods
JP5169343B2 (en) * 2008-03-14 2013-03-27 株式会社デンソー Coating forming method, coating forming apparatus and polymerization method
JP5089521B2 (en) * 2008-07-31 2012-12-05 学校法人 中村産業学園 Powder plasma processing method
DE102008052102B4 (en) * 2008-10-20 2012-03-22 INPRO Innovationsgesellschaft für fortgeschrittene Produktionssysteme in der Fahrzeugindustrie mbH Device for pre- and / or after-treatment of a component surface by means of a plasma jet
CN102223972A (en) * 2008-10-24 2011-10-19 普里梅精密材料有限公司 Group iva small particle compositions and related methods
US20100151114A1 (en) * 2008-12-17 2010-06-17 Zimmer, Inc. In-line treatment of yarn prior to creating a fabric
JP2012514060A (en) * 2008-12-24 2012-06-21 イントリンジック マテリアルズ リミテッド Fine particles
WO2010105829A1 (en) * 2009-03-19 2010-09-23 Anthony Herbert Apparatus and method for deposition of functional coatings
GB0906091D0 (en) 2009-04-07 2009-05-20 Snowball Malcolm R None invasive disinfector
US8642139B2 (en) * 2009-06-09 2014-02-04 Toyota Motor Engineering & Manufacturing North America, Inc. Process to make structured particles
US9243475B2 (en) 2009-12-08 2016-01-26 Baker Hughes Incorporated Extruded powder metal compact
US10240419B2 (en) 2009-12-08 2019-03-26 Baker Hughes, A Ge Company, Llc Downhole flow inhibition tool and method of unplugging a seat
EP2424336A1 (en) 2010-08-26 2012-02-29 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Plasma powder processing apparatus and method
EP2611948A2 (en) 2010-09-01 2013-07-10 Facultés Universitaires Notre-Dame de la Paix Method for depositing nanoparticles on substrates
US20120109301A1 (en) 2010-11-03 2012-05-03 Zimmer, Inc. Modified Polymeric Materials And Methods Of Modifying Polymeric Materials
DE102010044114A1 (en) * 2010-11-18 2012-05-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for joining substrates and composite structure obtainable therewith
WO2012123530A1 (en) * 2011-03-16 2012-09-20 Reinhausen Plasma Gmbh Coating, and method and device for coating
US8631876B2 (en) 2011-04-28 2014-01-21 Baker Hughes Incorporated Method of making and using a functionally gradient composite tool
US9080098B2 (en) 2011-04-28 2015-07-14 Baker Hughes Incorporated Functionally gradient composite article
CN103766000B (en) * 2011-06-03 2018-04-10 株式会社和广武 The manufacture method of CVD device and cvd film
GB201110282D0 (en) * 2011-06-17 2011-08-03 Linde Ag Device for providing a flow of plasma
US9139928B2 (en) 2011-06-17 2015-09-22 Baker Hughes Incorporated Corrodible downhole article and method of removing the article from downhole environment
US9707739B2 (en) 2011-07-22 2017-07-18 Baker Hughes Incorporated Intermetallic metallic composite, method of manufacture thereof and articles comprising the same
US9643250B2 (en) 2011-07-29 2017-05-09 Baker Hughes Incorporated Method of controlling the corrosion rate of alloy particles, alloy particle with controlled corrosion rate, and articles comprising the particle
US8581496B2 (en) * 2011-07-29 2013-11-12 Oaks Plasma, LLC. Self-igniting long arc plasma torch
US9833838B2 (en) 2011-07-29 2017-12-05 Baker Hughes, A Ge Company, Llc Method of controlling the corrosion rate of alloy particles, alloy particle with controlled corrosion rate, and articles comprising the particle
US9033055B2 (en) 2011-08-17 2015-05-19 Baker Hughes Incorporated Selectively degradable passage restriction and method
US9109269B2 (en) 2011-08-30 2015-08-18 Baker Hughes Incorporated Magnesium alloy powder metal compact
US9856547B2 (en) 2011-08-30 2018-01-02 Bakers Hughes, A Ge Company, Llc Nanostructured powder metal compact
US9090956B2 (en) 2011-08-30 2015-07-28 Baker Hughes Incorporated Aluminum alloy powder metal compact
US9643144B2 (en) * 2011-09-02 2017-05-09 Baker Hughes Incorporated Method to generate and disperse nanostructures in a composite material
CN102325422A (en) * 2011-09-13 2012-01-18 青岛佳明测控仪器有限公司 Flat plate type totally-sealed low-temperature plasma excitation source
WO2013040481A1 (en) 2011-09-15 2013-03-21 Cold Plasma Medical Technologies, Inc. Cold plasma sterilization devices and associated methods
CN102333410B (en) * 2011-09-16 2013-02-06 西安交通大学 Atmospheric pressure cold plasma jet device for etching photoresist materials
CN102361531B (en) * 2011-10-26 2013-07-03 西安电子科技大学 Device and method for generating large-area, uniform and non-magnetized plasmas
JP6083093B2 (en) * 2011-11-11 2017-02-22 国立大学法人佐賀大学 Plasma generator
JP2013144766A (en) * 2011-12-16 2013-07-25 Meiritsu Component Kk Surface modifier
RU2477763C1 (en) * 2012-01-11 2013-03-20 Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Сибирский Федеральный Университет" (Сфу) Method for obtaining polymer nanocomposite material
US9010416B2 (en) 2012-01-25 2015-04-21 Baker Hughes Incorporated Tubular anchoring system and a seat for use in the same
US9605508B2 (en) 2012-05-08 2017-03-28 Baker Hughes Incorporated Disintegrable and conformable metallic seal, and method of making the same
US10526707B2 (en) * 2012-08-29 2020-01-07 The University Of Tokyo Heat exchanger type reaction tube
KR101300627B1 (en) * 2012-09-17 2013-08-28 김재천 Surface modification by low-temperature plasma treatment expandable polystyrene resin particle fabrication method
KR101428524B1 (en) * 2012-12-10 2014-08-11 한국기초과학지원연구원 Plasma equipment for treating powder
WO2014106256A1 (en) * 2012-12-31 2014-07-03 Cold Plasma Medical Technologies, Inc. Apparatus for cold plasma bromhidrosis treatment
US9994683B2 (en) * 2013-03-15 2018-06-12 Kettering University Method and apparatus for surface chemical functionalization of powders and nanoparticles
CN103235244B (en) * 2013-04-02 2016-08-10 广东工业大学 A kind of dielectric barrier discharge circuit parameter detection device and detection method
KR101538388B1 (en) * 2013-06-11 2015-07-22 이이쿠보 유이치 Dielectric Barrier Discharge Reactor for making Disilane, Trisilane and Tetrasilane from Silane
KR20150002350A (en) * 2013-06-28 2015-01-07 삼성전기주식회사 Manufacturing method of metal nanopowder by wire explosion and apparatus for manufacturing the same
CN103442509A (en) * 2013-08-24 2013-12-11 大连海事大学 Reciprocating type multi-ionization-cavity atmospheric-pressure unbalance plasma reactor
US9816339B2 (en) 2013-09-03 2017-11-14 Baker Hughes, A Ge Company, Llc Plug reception assembly and method of reducing restriction in a borehole
US9437401B2 (en) 2013-12-20 2016-09-06 Plasmology4, Inc. System and method for plasma treatment using directional dielectric barrier discharge energy system
US11802337B1 (en) 2014-01-28 2023-10-31 United States of America as Administrator of NASA Atmospheric pressure plasma based fabrication process of printable electronics and functional coatings
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
WO2015127174A1 (en) 2014-02-21 2015-08-27 Terves, Inc. Fluid activated disintegrating metal system
US9550694B2 (en) 2014-03-31 2017-01-24 Corning Incorporated Methods and apparatus for material processing using plasma thermal source
US9533909B2 (en) 2014-03-31 2017-01-03 Corning Incorporated Methods and apparatus for material processing using atmospheric thermal plasma reactor
WO2016037304A1 (en) 2014-09-08 2016-03-17 GM Global Technology Operations LLC Coating particles of active electrode material for lithium secondary batteries
CN104284505A (en) * 2014-10-27 2015-01-14 核工业西南物理研究院 Normal-pressure low-temperature plasma running water form powder material modifying system
CN104302083B (en) * 2014-10-27 2017-01-25 核工业西南物理研究院 Streamlined powder material modification device for graft polymerization of low-temperature plasma under normal pressure
US20160200618A1 (en) * 2015-01-08 2016-07-14 Corning Incorporated Method and apparatus for adding thermal energy to a glass melt
US9910026B2 (en) 2015-01-21 2018-03-06 Baker Hughes, A Ge Company, Llc High temperature tracers for downhole detection of produced water
US10420199B2 (en) 2015-02-09 2019-09-17 Applied Quantum Energies, Llc Methods and apparatuses for treating agricultural matter
KR101514195B1 (en) * 2015-02-17 2015-04-23 주식회사 에코에너젠 Energy-Saving Type Dielectric Barrier Discharge Plasma NOx Reduction Equipment
MX2017010952A (en) * 2015-02-27 2018-06-06 Imerys Graphite & Carbon Switzerland Ltd Nanoparticle surface-modified carbonaceous material and methods for producing such material.
US10378303B2 (en) 2015-03-05 2019-08-13 Baker Hughes, A Ge Company, Llc Downhole tool and method of forming the same
US10221637B2 (en) 2015-08-11 2019-03-05 Baker Hughes, A Ge Company, Llc Methods of manufacturing dissolvable tools via liquid-solid state molding
JP6006393B1 (en) * 2015-10-09 2016-10-12 アルファ株式会社 Plasma processing equipment
JP6618772B2 (en) * 2015-11-06 2019-12-11 エア・ウォーター株式会社 Atmospheric pressure plasma processing equipment
FR3043679B1 (en) * 2015-11-12 2021-07-23 Aptar Stelmi Sas PROCESS FOR TREATING AN ELASTOMERIC PACKAGING ELEMENT, AND PACKAGING ELEMENT THUS TREATED.
US10440808B2 (en) 2015-11-17 2019-10-08 Southwest Research Institute High power impulse plasma source
US10016810B2 (en) 2015-12-14 2018-07-10 Baker Hughes, A Ge Company, Llc Methods of manufacturing degradable tools using a galvanic carrier and tools manufactured thereof
JP6722461B2 (en) * 2016-01-25 2020-07-15 日本ニューマチック工業株式会社 Powder processing apparatus and method
US10354845B2 (en) * 2016-02-18 2019-07-16 Southwest Research Institute Atmospheric pressure pulsed arc plasma source and methods of coating therewith
US11241833B2 (en) * 2016-03-09 2022-02-08 Universities Space Research Association 3D printed electronics using directional plasma jet
US10995406B2 (en) * 2016-04-01 2021-05-04 Universities Space Research Association In situ tailoring of material properties in 3D printed electronics
KR101877498B1 (en) * 2016-05-09 2018-08-22 국민대학교 산학협력단 magnetic nano-paticle and method of manufacturing for magnetic nano-particle
KR101877497B1 (en) * 2016-05-09 2018-08-23 국민대학교 산학협력단 Method for analyzing magnetic nano-particle using mossabuer spectroscopy, Method of manufacturing for magnetic nano-particle using mossabuer spectroscopy and magnetic nano-particle
LU93222B1 (en) * 2016-09-15 2018-04-11 Luxembourg Inst Science & Tech List Post-discharge plasma coating device for wired substrates
CN106714436A (en) * 2016-12-15 2017-05-24 南京克普医疗科技有限公司 Normal-temperature atmospheric-pressure plasma discharge electrode
TWM541176U (en) * 2016-12-21 2017-05-01 財團法人工業技術研究院 Apparatus for producing inorganic powder and apparatus for producing and classifying inorganic powder
TWI620228B (en) 2016-12-29 2018-04-01 財團法人工業技術研究院 Plasma treatment apparatus and plasma treatment method
CA3012511A1 (en) 2017-07-27 2019-01-27 Terves Inc. Degradable metal matrix composite
SG11202002725UA (en) 2017-10-01 2020-04-29 Space Foundry Inc Modular print head assembly for plasma jet printing
WO2019180839A1 (en) * 2018-03-20 2019-09-26 株式会社Ｆｕｊｉ Plasma device, plasma generation method
KR102066342B1 (en) * 2018-03-23 2020-01-14 한양대학교 산학협력단 Plasma generator
CN108530320B (en) * 2018-06-05 2020-12-01 合肥碳艺科技有限公司 Method for preparing hexacyanobenzene by non-thermal plasma method
RU188618U1 (en) * 2018-10-09 2019-04-18 Федеральное государственное бюджетное образовательное учреждение высшего образования "Липецкий государственный технический университет" (ЛГТУ) ELECTRIC ARC PLASMOTRON
AU2019364543A1 (en) 2018-10-24 2021-05-27 Atmospheric Plasma Solutions, Inc. Plasma source and method for preparing and coating surfaces using atmospheric plasma pressure waves
ES2880251T3 (en) * 2018-10-26 2021-11-24 Bonetto S R L Apparatus for plasma treatment of granular polymeric material
TWI685280B (en) * 2019-01-08 2020-02-11 明志科技大學 Air plasma surface treatment apparatus for surface modification of tube inner wall by grafting
RU2715054C1 (en) * 2019-04-15 2020-02-25 Федеральное государственное бюджетное образовательное учреждение высшего образования "Липецкий государственный технический университет" (ЛГТУ) Electric arc plasmatron
LU101177B1 (en) 2019-04-16 2020-10-16 Delmee Maxime Functionalized metal powders by small particles made by non-thermal plasma glow discharge for additive manufacturing applications
RU2713736C1 (en) * 2019-06-17 2020-02-07 Виктор Николаевич Мещеряков Electric arc plasmatron for combustion of solid wastes
CN112543541A (en) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 Gas discharge device with interactive electric field
CN112582164A (en) * 2019-09-29 2021-03-30 京磁材料科技股份有限公司 Sintered Nd-Fe-B rapid hardening alloy Nd-rich phase grain boundary doping method
JP6871556B2 (en) * 2019-12-02 2021-05-12 アルファ株式会社 Plasma processing equipment and plasma torch
KR102305666B1 (en) * 2020-01-22 2021-09-28 한국핵융합에너지연구원 Plasma surface treatment device of conductive powder
WO2022071823A1 (en) * 2020-09-30 2022-04-07 Siemens Energy Global Gmbh & Go. Kg A spherical carbide-coated metal powder and method for production thereof
CN112548089B (en) * 2020-11-04 2022-03-29 华南理工大学 Application of discharge plasma modification method in treatment of spherical/quasi-spherical metal powder prepared by atomization method
CN112958107B (en) * 2021-02-05 2022-11-29 山东省科学院新材料研究所 Ozone oxidation catalytic material and preparation method and application thereof
CN113368897B (en) * 2021-04-29 2023-09-26 西安交通大学 High-activity alumina-supported platinum catalyst and preparation method and application thereof
CN114263035A (en) * 2021-12-06 2022-04-01 北京天恒盛通科技发展有限公司 Water cooling tunnel type continuous plasma device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2244749A1 (en) * 1996-02-06 1997-08-14 E.I. Du Pont De Nemours And Company Treatment of deagglomerated particles with plasma-activated species
US6543460B1 (en) * 1999-06-24 2003-04-08 Wisconsin Alumni Research Foundation Cold-plasma treatment of seeds to remove surface materials
US6649222B1 (en) * 1998-09-07 2003-11-18 The Procter & Gamble Company Modulated plasma glow discharge treatments for making superhydrophobic substrates

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176938A (en) 1988-11-23 1993-01-05 Plasmacarb Inc. Process for surface treatment of pulverulent material
SU1620210A1 (en) 1989-01-13 1991-01-15 Московский институт стали и сплавов Arrangement for cladding pulverulent materials with carbonyl-forming metals
JP2967133B2 (en) 1990-07-25 1999-10-25 イーシー化学株式会社 Powder surface treatment method
JP3413661B2 (en) * 1991-08-20 2003-06-03 株式会社ブリヂストン Surface treatment method and apparatus
JP3280433B2 (en) 1992-10-09 2002-05-13 株式会社日清製粉グループ本社 Fiber or woven fabric in which ultrafine particles are uniformly dispersed and adhered to the surface, method for producing the same, and fiber-reinforced composite material using the same
JP3064182B2 (en) 1994-06-14 2000-07-12 松下電工株式会社 Atmospheric pressure plasma powder processing method and apparatus
EP0880562B1 (en) * 1996-02-06 2000-12-06 E.I. Du Pont De Nemours And Company Treatment of deagglomerated particles with plasma-activated species
IL122300A (en) * 1997-11-25 2005-09-25 Rafael Armament Dev Authority Modular dielectric barrier discharge device for pollution abatement
EP0985741A1 (en) 1998-09-07 2000-03-15 The Procter & Gamble Company Modulated plasma glow discharge treatments for making super hydrophobic substrates
US20010053742A1 (en) 1998-12-18 2001-12-20 Ronald D. Knudsen Catalyst and processes for olefin trimerization
JP2002110397A (en) 2000-09-27 2002-04-12 Sekisui Chem Co Ltd Generating method of normal pressure pulse plasma
US6685803B2 (en) * 2001-06-22 2004-02-03 Applied Materials, Inc. Plasma treatment of processing gases
US20030157000A1 (en) * 2002-02-15 2003-08-21 Kimberly-Clark Worldwide, Inc. Fluidized bed activated by excimer plasma and materials produced therefrom
JP2005322416A (en) 2003-05-01 2005-11-17 Gunma Univ Atmospheric pressure low-temperature plasma device and surface treating method
US7758928B2 (en) 2003-10-15 2010-07-20 Dow Corning Corporation Functionalisation of particles
US7615931B2 (en) * 2005-05-02 2009-11-10 International Technology Center Pulsed dielectric barrier discharge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2244749A1 (en) * 1996-02-06 1997-08-14 E.I. Du Pont De Nemours And Company Treatment of deagglomerated particles with plasma-activated species
US6649222B1 (en) * 1998-09-07 2003-11-18 The Procter & Gamble Company Modulated plasma glow discharge treatments for making superhydrophobic substrates
US6543460B1 (en) * 1999-06-24 2003-04-08 Wisconsin Alumni Research Foundation Cold-plasma treatment of seeds to remove surface materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yasushi Sawada et al.Plasma-polymerized tetrafluoroethylene coatings on silica particles by atmospheric-pressure glow discharge.《Powder Technology》.1997,(第90期),245-250. *

Also Published As

Publication number Publication date
US20080145553A1 (en) 2008-06-19
RU2009107047A (en) 2010-09-10
RU2462534C2 (en) 2012-09-27
WO2008014607A1 (en) 2008-02-07
JP5260515B2 (en) 2013-08-14
CA2659298A1 (en) 2008-02-07
EP2052097A4 (en) 2010-10-20
EP2052097B1 (en) 2016-12-07
JP2009544854A (en) 2009-12-17
DE07785015T1 (en) 2009-11-26
CN101573467A (en) 2009-11-04
US8263178B2 (en) 2012-09-11
CA2659298C (en) 2012-03-06
KR101428679B1 (en) 2014-08-08
WO2008014607A8 (en) 2008-04-24
KR20090047503A (en) 2009-05-12
EP2052097A1 (en) 2009-04-29

Similar Documents

Publication Publication Date Title
CN101573467B (en) Plasma surface treatment using dielectric barrier discharges
US20240010499A1 (en) Apparatus and method for plasma synthesis of graphitic products including graphene
US20120261391A1 (en) Atmospheric pressure plasma method for producing surface-modified particles and coatings
Alexandrov et al. Chemical vapor deposition enhanced by atmospheric pressure non‐thermal non‐equilibrium plasmas
CN114229820B (en) Seed-free particles with carbon allotropes
KR101542309B1 (en) Production of ultrafine particles in a plasma system having controlled pressure zones
WO2007007995A1 (en) Surface coating method for hydrophobic and superhydrophobic treatment in atmospheric pressure plasma
US20120094033A1 (en) Nanoparticles with grafted organic molecules
EP2114577B1 (en) System and method for electrostatically depositing particles
Saito et al. Microstructured SiOx thin films deposited from hexamethyldisilazane and hexamethyldisiloxane using atmospheric pressure thermal microplasma jet
CN114728338A (en) Fine particle manufacturing device and fine particle manufacturing method
CN111727096B (en) Process for producing silver microparticles
CN113237867B (en) Device and method for preparing surface enhanced Raman substrate by coupling micro-fluidic technology and plasma technology
WO2003017737A2 (en) Cascade arc plasma and abrasion resistant coatings made therefrom
WO2019146414A1 (en) Copper microparticles
Nessim et al. In-flight coating of nanoparticles in atmospheric-pressure DBD torch plasmas
Tyurikov et al. Corona discharge plasma application for the deposition of nanocomposite coatings
EP3565386A1 (en) Method for plasma powder treatment and coating
RU2414993C2 (en) Method of producing nanopowder using low-pressure transformer-type induction charge and device to this end
Bouyer et al. Thermal plasma processing of nanostructured Si-based ceramic materials
Wang et al. A new method for deposition nitrogen‐doped TiO2 nanofibers with mixed phases of anatase and rutile
WO2023122202A1 (en) Systems and methods for producing carbon solids
CN117550590A (en) Graphene preparation method and preparation device
Qin Synthesis of organic layer-coated metal nanoparticles in a dual-plasma process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121128

Termination date: 20170731

CF01 Termination of patent right due to non-payment of annual fee